Tomas Remenyi

Modern sampling and analytical methods for the determination of trace elements in marine particulate material using magnetic sector inductively coupled plasma-mass spectrometry

Trace elements often limit phytoplankton growth in the ocean, and the quantification of particulate forms is essential to fully understand their biogeochemical cycling. There is presently a lack of reliable measurements on the trace elemental content of marine particles, in part due to the inadequacies of the sampling and analytical methods employed. Here we report on the development of a series of state-of-the-art trace metal clean methods to collect and process oceanic particulate material in open-ocean and sea ice environments, including sampling, size-fractionated filtration, particle digestions and analysis by magnetic sector inductively coupled plasma-mass spectrometry (ICP-MS). Particular attention was paid to the analysis of certified reference materials (CRMs) and field blanks, which are typically the limiting factor for the accurate analysis of low concentrations of trace metals in marine particulate samples. Theoretical detection limits (3 s of the blank) were low for all 17 elements considered, and varied according to filter material and porosity (sub-microg L(-1) for polycarbonate filters and 1-2 microg L(-1) for quartz and polyester filters). Analytical accuracy was verified using fresh water CRMs, with excellent recoveries noted (93-103%). Digestion efficiencies for various acid combinations were assessed using sediment and plankton CRMs. Using nitric acid only, good recoveries (79-90%) were achieved for Mo, Cd, Ba, Pb, Mn, Fe, Co, Ni, Cu, Zn and Ga. The addition of HF was necessary for the quantitative recovery of the more refractory trace elements such as U, Al, V and Cr. Bioactive elements such as P can also be analysed and used as a biomass normaliser. Our developed sampling and analytical methods proved reliable when applied during two major field programs in both the open Southern Ocean and Antarctic sea ice environments during the International Polar Year in 2007. Trace elemental data are presented for particulate samples collected in both suspended and sinking marine material, and also within sea ice cores.

Investigation of polar organic solvents compatible with Corona Charged Aerosol Detection and their use for the determination of sugars by hydrophilic interaction liquid chromatography.

A range of organic solvents (ethanol, isopropanol and acetone) has been investigated as alternatives to acetonitrile and methanol when used in conjunction with Corona Charged Aerosol Detection (Corona CAD). These solvents have been evaluated with regard to their effect on the response of the Corona CAD. Three dimensional response surfaces were constructed using raw data showing the relationship between detector response, analyte concentration and percentage of organic solvent in the mobile phase, using sucralose or quinine as the test analyte. The detector response was non-linear in terms of analyte concentration for all solvents tested. However, detector response varied in an approximately linear manner with percentage of organic solvent over the range 0-40% for ethanol or isopropanol and 0-80% for acetone and methanol. The chromatographic performance of the various solvents when used as aqueous-organic mobile phases was evaluated for isocratic and gradient separations of sugars and sugar alcohols by hydrophilic interaction liquid chromatography (HILIC) using an Asahipak NH2P-504E column coupled with Corona CAD detection. It was found that whilst acetonitrile provided the highest column efficiencies and lowest detection limits of the solvents studied, acetone also performed well and could be used to resolve the same number of analytes as was possible with acetonitrile. Typical efficiencies and detection limits of 5330 plates m(-1) and 1.25 μg mL(-1), respectively, were achieved when acetone was used as the organic modifier. Acetone was utilised successfully as an organic modifier in the HILIC separation of carbohydrates in a beer sample and also for a partially digested dextran sample.

Microplate-reader method for the rapid analysis of copper in natural waters with chemiluminescence detection

We have developed a method for the determination of copper in natural waters at nanomolar levels. The use of a microplate-reader minimizes sample processing time (~25 s per sample), reagent consumption (~120 μL per sample), and sample volume (~700 μL). Copper is detected by chemiluminescence. This technique is based on the formation of a complex between copper and 1,10-phenanthroline and the subsequent emission of light during the oxidation of the complex by hydrogen peroxide. Samples are acidified to pH 1.7 and then introduced directly into a 24-well plate. Reagents are added during data acquisition via two reagent injectors. When trace metal clean protocols are employed, the reproducibility is generally less than 7% on blanks and the detection limit is 0.7 nM for seawater and 0.4 nM for freshwater. More than 100 samples per hour can be analyzed with this technique, which is simple, robust, and amenable to at-sea analysis. Seawater samples from Storm Bay in Tasmania illustrate the utility of the method for environmental science. Indeed other trace metals for which optical detection methods exist (e.g., chemiluminescence, fluorescence, and absorbance) could be adapted to the microplate-reader.

Fast and sensitive determination of aluminium with RP-HPLC using an ultra-short monolithic column

A fast and sensitive reversed-phase high-performance liquid-chromatographic method for determination of aluminium in aqueous samples has been developed. The fluorescent aluminium-lumogallion complex (λex 505 nm, λem 574 nm), was formed with a pre-column reagent and then separated on a Chromolith® RP-18e Guard column using a two-tiered, stepped gradient program, with matrix elimination (5/95 (v/v) methanol/water), followed by elution (90/10 (v/v) methanol/water). This method achieved a run time of 2.5 min without compromising sensitivity (limit of detection = 5.6 × 10−10 M, limit of quantification = 7.2 × 10−7 M), precision (3.5% at 3.71 × 10−6 M) or accuracy (recovery = 97.5% ± 3.2%, n = 5, P = 0.95). This represents an improvement in run time by >50% compared to the fastest previously published method [Lee et al., Clin. Chem., 1996, 42, 1405–1411]. This method uses MES buffer (2-(N-morpholino)ethanesulfonic acid), which compared to other buffers is more easily purified, does not complex with aluminium, and can be used in lower concentrations. This method was applied to analysis of: deionised water for column comparison; seawater for matrix interference effects; and tea-infusion for calibration and recovery studies.

Biological responses to the press and pulse of climate trends and extreme events

The interaction of gradual climate trends and extreme weather events since the turn of the century has triggered complex and, in some cases, catastrophic ecological responses around the world. We illustrate this using Australian examples within a press–pulse framework. Despite the Australian biota being adapted to high natural climate variability, recent combinations of climatic presses and pulses have led to population collapses, loss of relictual communities and shifts into novel ecosystems. These changes have been sudden and unpredictable, and may represent permanent transitions to new ecosystem states without adaptive management interventions. The press–pulse framework helps illuminate biological responses to climate change, grounds debate about suitable management interventions and highlights possible consequences of (non-) intervention.A press–pulse framework is used to understand the interactive ecological effects of gradual climate trends and extreme weather events. Australian case studies include population collapses, loss of relictual communities and novel ecosystems.

Unusual suspects in the usual places: a phylo-climatic framework to identify potential future invasive species

A framework for identifying species that may become invasive under future climate conditions is presented, based on invader attributes and biogeography in combination with projections of future climate. We illustrate the framework using the CLIMEX niche model to identify future climate suitability for three species of Hawkweed that are currently present in the Australian Alps region and related species that are present in the neighbouring region. Potential source regions under future climate conditions are identified, and species from those emerging risk areas are identified. We use dynamically downscaled climate projections to complement global analyses and provide fine-scale projections of suitable climate for current and future (2070–2099) conditions at the regional scale. Changing climatic conditions may reduce the suitability for some invasive species and improve it for others. Invasive species with distributions strongly determined by climate, where the projected future climate is highly suitable, are those with the greatest potential to be future invasive species in the region. As the Alps region becomes warmer and drier, many more regions of the world become potential sources of invasive species, although only one additional species of Hawkweed is identified as an emerging risk. However, in the longer term, as the species in these areas respond to global climate change, the potential source areas contract again to match higher altitude regions. Knowledge of future climate suitability, based on species-specific climatic tolerances, is a useful step towards prioritising management responses such as targeted eradication and early intervention to prevent the spread of future invasive species.

Author Correction: Biological responses to the press and pulse of climate trends and extreme events

In the version of this Perspective originally published, affiliations 1 and 4 ware incorrect, and should have read: “1Antarctic Climate & Ecosystems CRC, University of Tasmania, Hobart, Tasmania, Australia” and “4Centre for Water, Climate and Land (CWCL), University of Newcastle, Callaghan, NSW, Australia”. These have been corrected in the online versions of this Perspective.

The relationship between irrigation-induced electrical loads and antecedent weather conditions in Tasmania, Australia

Over the past decade in Australia, there has been a general trend towards the introduction of electrical motors to operate irrigation pumps. While electrical motors provide many advantages over the alternatives, electrical loads can aggregate in some areas to become large peaks, which challenge the existing electrical distribution networks. This is especially true during extreme hot or dry periods, when irrigators collectively demand significant electrical resources at the same time. While there is an inherent link between weather conditions and the amount of electricity used for irrigation, this relationship is poorly understood. Previous studies have either focused on localised data related to concurrent temperature, rainfall and soil moisture, or they have annualised summaries over large areas. In this study, we compare intensive irrigation periods with the drought factor at a case study irrigation scheme in Tasmania, Australia, finding a strong relationship between electrical load and periods when the drought factor is > 6. This relatively simple relationship may be useful for managers of electricity supply and distribution, managers of water resources, and irrigators, as it may be used to minimise the risk of exceeding the capacity of the electricity network, improve water availability and optimise irrigation scheduling.

Heatwave and health impact research: a global review

Background: Observed increases in the frequency and intensity of heatwave events, together with the projected acceleration of these events worldwide, has led to a rapid expansion in research on the health impacts of extreme heat. Objective: To examine how research on heatwaves and their health‐related impact is distributed globally. Methods: A systematic review was undertaken. Four online databases were searched for articles examining links between specific historical heatwave events and their impact on mortality or morbidity. The locations of these events were mapped at a global scale, and compared to other known characteristics that influence heat‐related illness and death. Results: When examining the location of heatwave and health impact research worldwide, studies were concentrated on mid‐latitude, high‐income countries of low‐ to medium‐population density. Regions projected to experience the most extreme heatwaves in the future were not represented. Furthermore, the majority of studies examined mortality as a key indicator of population‐wide impact, rather than the more sensitive indicator of morbidity. Conclusion: While global heatwave and health impact research is prolific in some regions, the global population most at risk of death and illness from extreme heat is under‐represented. Heatwave and health impact research is needed in regions where this impact is expected to be most severe. HIGHLIGHTSHeatwave and health impact research is not distributed evenly across the globe.Regions most at risk from heatwaves and health impact are under‐represented in the research.Research focussing on morbidity is under‐represented compared with mortality‐focussed research.